2,6-diarylpiperidin-1-yl substituted 2-butene stabilizers

ABSTRACT

2,6-Diarylpiperidin-1-yl substituted 2-butene stabilizers of the formula I or II 
     
         T--CH.sub.2 --CH═CH--CH.sub.2 --T                      (I) 
    
     
         T--CH.sub.2 --CH═CH--CH.sub.2 --N(E.sub.1)(E.sub.2)    (II) 
    
     where T is a 2,6-diarylpiperidin-1-yl moiety and E 1  and E 2  are independently alkyl, cycloalkyl, aralkyl or aryl, are effective in stabilizing organic materials against the deleterious effects of oxygen, heat and actinic radiation.

The present invention pertains to novel 2,6-diarylpiperidin-1-ylsubstituted 2-butene compounds and their use as stabilizers for variousorganic materials subject to the deleterious effects of oxygen, heat oractinic radiation. The instant compounds provide good retention ofpolymer physical properties during long-term thermooxidative stress.

BACKGROUND OF THE INVENTION

Substituted 1,4-diamino-2-butene compounds are known in the art wherethe substitution on the N-atoms is alkyl or benzyl, but their use asstabilizers is not disclosed or suggested.

When such substitution is aryl, British Patent No. 1,438,482 generallydescribes N,N,N',N'-tetraaryl-2-butene-1,4-diamine as stabilizers forlubricant compositions, but does not specifically disclose suchcompounds. British 1,438,482 does not suggest that such aryl substitutedcompounds can provide effective antioxidant protection to syntheticpolymers.

The compounds of this invention and their use as stabilizers for organicmaterials subject to degradation by oxygen, heat or light are notdisclosed or suggested in the prior art.

OBJECTS OF THE INVENTION

One object of this invention is to provide new substituted 2-butenecompounds which are useful stabilizers for various substrates.

Another object of the invention is to provide synthetic polymercompositions stabilized against the deleterious effects of oxygen, heatand light by incorporating therein an effective amount of an instantcompound.

DETAILED DISCLOSURE

The instant invention pertains to novel compounds of formula I or II

    T--CH.sub.2 --CH═CH--CH.sub.2 --T                      (I)

    T--CH.sub.2 --CH═CH--CH.sub.2 --N(E.sub.1)(E.sub.2)    (II)

wherein

E₁ and E₂ are independently alkyl of 1 to 30 carbon atoms, said alkylterminated with cycloalkyl of 5 to 12 carbon atoms, said alkylterminated with --CN, --OR₁₆, --NR₁₇ R₁₈, --SR₁₉, --COOR₂₀ or --CONR₂₁R₂₂, where R₁₆, R₁₇, R₁₈, R₁₉ and R₂₀ are independently alkyl of 1 to 20carbon atoms or alkenyl of 3 to 18 carbon atoms, and R₂₁ and R₂₂ areindependently hydrogen or the same meaning as R₁₆ ; or said alkylinterrupted by one or more --O--, --S--, --SO--, --SO₂ --, --CO--,--COO--, --OCO--, --CONR₂₃ --, --NR₂₃ CO-- or --NR₂₄ -- where R₂₃ andR₂₄ have the same meaning as R₂₁ ; alkenyl of 3 to 20 carbon atoms;aralkyl of 7 to 15 carbon atoms or said aralkyl substituted on the arylring by one to three groups selected from alkyl of 1 to 12 carbon atoms,--CN, --NO₂, halogen, --OR₁₆, --NR₁₇ R₁₈, --SR₁₉, --COOR₂₀ or --CONR₂₁R₂₂, or aryl of 6 to 10 carbon atoms or said aryl substituted by one tothree substituents selected from the group consisting of alkyl of 1 to20 carbon atoms, cycloalkyl of 5 to 12 carbon atoms and aralkyl of 7 to15 carbon atoms;

T is a group of formula III, IV, V or VI ##STR1## where Ar₁ and Ar₂ areindependently aryl of 6 to 10 carbon atoms; or said aryl substituted byone to three substituents selected from the group consisting of alkyl of1 to 20 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of7 to 15 carbon atoms, --COOG₁ where G₁ is hydrogen or alkyl of 1 to 20carbon atoms, --COG₂ where G₂ is alkyl of 1 to 20 carbon atoms, --NR₅ R₆where R₅ and R₆ are independently hydrogen or alkyl of 1 to 20 carbonatoms, --SG₃ where G₃ is aryl of 6 to 10 carbon atoms or alkyl of 1 to20 carbon atoms, --OH, --OCH₃, --CN, --CF₃, --NO₂, --F, --Cl, --Br or--I;

R₁, R₂, R₃ and R₄ are independently hydrogen; a linear or branched alkylof 1 to 30 carbon atoms; said alkyl terminated with --OR₇, --NR₈ R₉,--SR₁₀, --COOR₁₁ or --CONR₁₂ R₁₃, where R₇, R₈, R₉, R₁₀ and R₁₁ areindependently hydrogen, alkyl of 1 to 20 carbon atoms or alkenyl of 3 to18 carbon atoms, and R₁₂ and R₁₃ are independently hydrogen or the samemeaning as R₁₁ ; or said alkyl interrupted by one or more --O--, --S--,--SO--, --SO₂ --, --CO--, --COO--, --OCO--, --CONR₁₄ --, --NR₁₄ CO-- or--NR₁₅ -- where R₁₄ and R₁₅ have the same meaning as R₁₂ ; alkenyl of 3to 20 carbon atoms; or aryl of 6 to 10 carbon atoms;

L₁ is hydrogen, --OR₂₅ where R₂₅ is hydrogen or alkyl of 1 to 30 carbonatoms, --NR₂₆ R₂₇, --OCOR₂₈, --NCOR₂₉ where R₂₆, R₂₇, R₂₈ and R₂₉ havethe same meaning as R₂₅ ;

L₂ and L₃ are independently --Y₁ --R₃₀ or --Z₁ --R₃₁ where Y₁ and Z₁ areindependently --O--, --S-- or --NR₂₆ --, and R₃₀ and R₃₁ are hydrogen oralkyl of 1 to 30 carbon atoms; and

n is 0 or 1, Y₂ and Z₂ are independently --O--, --S-- or --NR₂₆ --, andR₃₂, R₃₃, R₃₄, R₃₅, R₃₆ and R₃₇ are independently hydrogen or alkyl of 1to 30 carbon atoms.

Preferably Ar₁ and Ar₂ are phenyl.

Preferably R₁, R₂, R₃ and R₄ are independently hydrogen or methyl, mostpreferably hydrogen.

Preferably E₁ and E₂ are each benzyl.

Preferably T is a structure of formula III where L₁ is hydrogen.

The instant invention also pertains to stabilized compositionscomprising

(a) an organic material subject to oxidative, thermal or actinicdegradation, and

(b) an effective stabilizing amount of a compound of formula I or II asdefined above.

The preparation of 2,6-diphenylpiperidine is described by V. Balaih etal., Indian J. Chem., 16B, 1065 (1978).

The compounds of formula I and formula II are conveniently prepared byreacting an appropriate secondary amine such as 2,6-diphenylpiperidinewith 1,4-but-2-enediol diacetate in the presence of a catalyst such astetrakis(triphenylphosphine)palladium(0) in an organic solvent such astetrahydrofuran.

The starting materials for making the instant compounds are largelyitems of commerce.

When any of Ar₁, Ar₂, R₁ to R₃₇, E₁, E₂, L₁, L₂, or G₁ to G₃ is alkyl,such alkyl groups are, for example, methyl, ethyl, isopropyl, n-butyl,tert-butyl, tert-amyl, 2-ethylhexyl, n-octyl, n-undecyl, lauryl,n-heptadecyl, n-octadecyl, eicosyl and tricontyl; when said radicals arecycloalkyl, they are, for example, cyclopentyl, cyclohexyl, cyclooctyland cyclododecyl; when said radicals are aralkyl, they are, for example,benzyl, phenethyl, a-methylbenzyl, a,a-dimethylbenzyl and1-naphthylmethyl; when said radicals are aryl, they are, for example,phenyl, naphthyl or when substituted by alkyl are, for example, tolyland xylyl; and when said radicals are alkyl interrupted by --O--, theyare, for example, 3-oxaamyl and 3,6-dioxaoctyl.

The compositions where component (a) is a synthetic polymer areespecially a part of this invention, most particularly when thesynthetic polymer is a polyolefin such as polypropylene or is anelastomer such as dynamically crosslinked polypropylene/nitrile rubber.

The instant compounds are effective stabilizers for synthetic polymerssubject to the deleterious effects of heat and/or oxygen especiallyduring processing at elevated temperatures.

In general polymers which can be stabilized include

1. Polymers of monoolefins and diolefins, for example polyethylene(which optionally can be crosslinked), polypropylene, polyisobutylene,polybutene-1, polymethylpentene-1, polyisoprene or polybutadiene, aswell as polymers of cycloolefins, for instance of cyclopentene ornorbornene.

2. Mixtures of the polymers mentioned under 1), for example mixtures ofpolypropylene with polyisobutylene.

3. Copolymers of monoolefins and diolefins with each other or with othervinyl monomers, such as, for example, ethylene/propylene,propylene/butene-1, propylene/isobutylene, ethylene/butene-1,propylene/butadiene, isobutylene/isoprene, ethylene/alkyl acrylates,ethylene/alkyl methacrylates, ethylene/vinyl acetate or ethylene/acrylicacid copolymers and their salts (ionomers) and terpolymers of ethylenewith propylene and a diene, such as hexadiene, dicyclopentadiene orethylidene-norbornene.

4. Polystyrene, poly-(p-methylstyrene).

5. Copolymers of styrene or methylstyrene with dienes or acrylicderivatives, such as, for example, styrene/butadiene,styrene/acrylonitrile, styrene/ethyl methacrylate,styrene/butadiene/ethyl acrylate, styrene/acrylonitrile/methyl acrylate;mixtures of high impact strength from styrene copolymers and anotherpolymer, such as, for example, from a polyacrylate, a diene polymer oran ethylene/propylene/diene terpolymer; and block polymers of styrene,such as, for example, styrene/butadiene/styrene,styrene/isoprene/styrene, styrene/ethylene/butylene/styrene orstyrene/ethylene/propylene/styrene.

6. Graft copolymers of styrene, such as, for example, styrene onpolybutadiene, styrene and acrylonitrile on polybutadiene, styrene andalkyl acrylates or methacrylates on polybutadiene, styrene andacrylonitrile on ethylene/propylene/diene terpolymers, styrene andacrylonitrile on polyacrylates or polymethacrylates, styrene andacrylonitrile on acrylate/butadiene copolymers, as well as mixturesthereof with the copolymers listed under 5), for instance the copolymermixtures known as ABS-, MBS-, ASA- or AES-polymers.

7. Halogen-containing polymers, such as polychloroprene, chlorinatedrubbers, chlorinated or sulfochlorinated polyethylene, epichlorohydrinhomo- and copolymers, polymers from halogen-containing vinyl compounds,as for example, polyvinylchloride, polyvinylidene chloride, polyvinylfluoride, polyvinylidene fluoride, as well as copolymers thereof, as forexample, vinyl chloride/vinylidene chloride, vinyl chloride/vinylacetate, vinylidene chloride/vinyl acetate copolymers, or vinylfluoride/vinyl ether copolymers.

8. Polymers which are derived from α,β-unsaturated acids and derivativesthereof, such as polyacrylates and polymethacrylates, polyacrylamide andpolyacrylonitrile.

9. Copolymers from the monomers mentioned under 8) with each other orwith other unsaturated monomers, such as, for instance,acrylonitrile/butadiene, acrylonitrile/alkyl acrylate,acrylonitrile/alkoxyalkyl acrylate or acrylonitrile/vinyl halogenidecopolymers or acrylonitrile/alkyl methacrylate/butadiene terpolymers.

10. Polymers which are derived from unsaturated alcohols and amines, oracyl derivatives thereof or acetals thereof, such as polyvinyl alcohol,polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinylmaleate, polyvinylbutyral, polyallyl phthalate or polyallyl-melamine.

11. Homopolymers and copolymers of cyclic ethers, such as polyalkyleneglycols, polyethylene oxide, polypropylene oxide or copolymers thereofwith bis-glycidyl ethers.

12. Polyacetals, such as polyoxymethylene and those polyoxymethyleneswhich contain ethylene oxide as comonomer.

13. Polyphenylene oxides and sulfides, and mixtures of polyphenyleneoxides with polystyrene.

14. Polyurethanes which are derived from polyethers, polyesters orpolybutadienes with terminal hydroxyl groups on the one side andaliphatic or aromatic polyisocyanates on the other side, as well asprecursors thereof (polyisocyanates, polyols or prepolymers).

15. Polyamides and copolyamides which are derived from diamines anddicarboxylic acids and/or from aminocarboxylic acids or thecorresponding lactams, such as polyamide 4, polyamide 6, polyamide 6/6,polyamide 6/10, polyamide 11, polyamide 12,poly-2,4,4-trimethylhexamethylene terephthalamide, poly-p-phenyleneterephthalamide or poly-m-phenylene isophthalamide, as well ascopolymers thereof with polyethers, such as for instance withpolyethylene glycol, polypropylene glycol or polytetramethylene glycols.

16. Polyureas, polyimides and polyamide-imides.

17. Polyesters which are derived from dicarboxylic acids and diolsand/or from hydroxycarboxylic acids or the corresponding lactones, suchas polyethylene terephthalate, polybutylene terephthalate,poly-1,4-dimethylol-cyclohexane terephthalate,poly-[2,2-(4-hydroxyphenyl)-propane] terephthalate andpolyhydroxybenzoates as well as block-copolyether-esters derived frompolyethers having hydroxyl end groups.

18. Polycarbonates.

19. Polysulfones, polyethersulfones and polyetherketones.

20. Crosslinked polymers which are derived from aldehydes on the onehand and phenols, ureas and melamines on the other hand, such asphenol/formaldehyde resins, urea/formaldehyde resins andmelamine/formaldehyde resins.

21. Drying and non-drying alkyd resins.

22. Unsaturated polyester resins which are derived from copolyesters ofsaturated and unsaturated dicarboxylic acids with polyhydric alcoholsand vinyl compounds as crosslinking agents, and also halogen-containingmodifications thereof of low flammability.

23. Thermosetting acrylic resins, derived from substituted acrylicesters, such as epoxy-acrylates, urethane-acrylates or polyesteracrylates.

24. Alkyd resins, polyester resins or acrylate resins in admixture withmelamine resins, urea resins, polyisocyanates or epoxide resins ascrosslinking agents.

25. Crosslinked epoxide resins which are derived from polyepoxides, forexample from bis-glycidyl ethers or from cycloaliphatic diepoxides.

26. Natural polymers, such as cellulose, rubber, gelatin and derivativesthereof which are chemically modified in a polymer homologous manner,such as cellulose acetates, cellulose propionates and cellulosebutyrates, or the cellulose ethers, such as methyl cellulose.

27. Mixtures of polymers as mentioned above, for example PP/EPDM,Polyamide 6/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS, PBTP/ABS.

28. Naturally occuring and synthetic organic materials which are puremonomeric compounds or mixtures of such compounds, for example mineraloils, animal and vegetable fats, oil and waxes, or oils, fats and waxesbased on synthetic esters (e.g. phthalates, adipates, phosphates ortrimellitates) and also mixtures of synthetic esters with mineral oilsin any weight ratios, which materials may be used as plasticizers forpolymers or as textile spinning oils, as well as aqueous emulsions ofsuch materials.

29. Aqueous emulsions of natural or synthetic rubber, e.g. natural latexor latices of carboxylated styrene/butadiene copolymers.

30. Polysiloxanes such as the soft, hydrophilic polysiloxanes described,for example, in U.S. Pat. No. 4,259,467; and the hardpolyorganosiloxanes described, for example, in U.S. Pat. No. 4,355,147.

31. Polyketimines in combination with unsaturated acrylicpolyacetoacetate resins or with unsaturated acrylic resins. Theunsaturated acrylic resins include the urethane acrylates, polyetheracrylates, vinyl or acryl copolymers with pendant unsaturated groups andthe acrylated melamines. The polyketimines are prepared from polyaminesand ketones in the presence of an acid catalyst.

32. Radiation curable compositions containing ethylenically unsaturatedmonomers or oligomers and a polyunsaturated aliphatic oligomer.

33. Epoxymelamine resins such as light-stable epoxy resins crosslinkedby an epoxy functional coetherified high solids melamine resin such asLSE-4103 (Monsanto).

In general, the compounds of the present invention are employed in fromabout 0.01 to about 5% by weight of the stabilized composition, althoughthis will vary with the particular substrate and application. Anadvantageous range is from about 0.5 to about 2%, and especially 0.1 toabout 1%.

The stabilizers of the instant invention may readily be incorporatedinto the organic polymers by conventional techniques, at any convenientstage prior to the manufacture of shaped articles therefrom. Forexample, the stabilizer may be mixed with the polymer in dry powderform, or a suspension or emulsion of the stabilizer may be mixed with asolution, suspension, or emulsion of the polymer. The resultingstabilized polymer compositions of the invention may optionally alsocontain from about 0.01 to about 5%, preferably from about 0.025 toabout 2%, and especially from about 0.1 to about 1% by weight of variousconventional additives, such as the materials listed below, or mixturesthereof.

1. Antioxidants

1.1. Alkylated monophenols, for example,

2,6-di-tert-butyl-4-methylphenol

2-tert.butyl-4,6-dimethylphenol

2,6-di-tert-butyl-4-ethylphenol

2,6-di-tert-butyl-4-n-butylphenol

2,6-di-tert-butyl-4-i-butylphenol

2,6-di-cyclopentyl-4-methylphenol

2-(α-methylcyclohexyl)-4,6-dimethylphenol

2,6-di-octadecyl-4-methylphenol

2,4,6-tri-cyclohexylphenol

2,6-di-tert-butyl-4-methoxymethylphenol

1.2. Alkylated hydroquinones, for example,

2,6-di-tert-butyl-4-methoxyphenol

2,5-di-tert-butyl-hydroquinone

2,5-di-tert-amyl-hydroquinone

2,6-diphenyl-4-octadecyloxyphenol

1.3. Hydroxylated thiodiphenyl ethers, for example,

2,2'-thio-bis-(6-tert-butyl-4-methylphenol)

2,2'-thio-bis-(4-octylphenol)

4,4'-thio-bis-(6-tert-butyl-3-methylphenol)

4,4'-thio-bis-(6-tert-butyl-2-methylphenol)

1.4. Alkylidene-bisphenols, for example,

2,2'-methylene-bis-(6-tert-butyl-4-methylphenol)

2,2'-methylene-bis-(6-tert-butyl-4-ethylphenol)

2,2'-methylene-bis-[4-methyl-6-(α-methylcyclohexyl)-phenol]

2,2'-methylene-bis-(4-methyl-6-cyclohexylphenol)

2,2'-methylene-bis-(6-nonyl-4-methylphenol)

2,2'-methylene-bis-[6-(α-methylbenzyl)-4-nonylphenol]

2,2'-methylene-bis-[6-(α,α-dimethylbenzyl)-4-nonylphenol]

2,2'-methylene-bis-(4,6-di-tert-butylphenol)

2,2'-ethylidene-bis-(4,6-di-tert-butylphenol)

2,2'-ethylidene-bis-(6-tert-butyl-4-isobutylphenol)

4,4'-methylene-bis-(2,6-di-tert-butylphenol)

4,4'-methylene-bis-(6-tert-butyl-2-methylphenol)

1,1-bis-(5-tert-butyl-4-hydroxy-2-methylphenyl-butane

2,6-di-(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol

1,1,3-tris-(5-tert-butyl-4-hydroxy-2-methylphenyl)-butane

1,1-bis-(5-tert-butyl-4-hydroxy-2-methylphenyl)-3-n-dodecylmercaptobutane

ethyleneglycol bis-[3,3-bis-(3'-tert-butyl-4'-hydroxyphenyl)-butyrate]

di-(3-tert-butyl-4-hydroxy-5-methylphenyl)-dicyclopentadiene

di-[2-(3'-tert-butyl-2'-hydroxy-5'-methyl-benzyl)-6-tert-butyl-4-methylphenyl]terephthalate.

1.5. Benzyl compounds, for example,

1,3,5-tri-(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene

di-(3,5-di-tert-butyl-4-hydroxybenzyl) sulfide

3,5-di-tert-butyl-4-hydroxybenzyl-mercapto-acetic acid isooctyl ester

bis-(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithiol terephthalate

1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate

1,3,5-tris-(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate

3,5-di-tert-butyl-4-hydroxybenzyl-phosphoric acid dioctadecyl ester

3,5-di-tert-butyl-4-hydroxybenzyl-phosphoric acid monoethyl ester,calcium-salt

1.6. Acylaminophenols, for example,

4-hydroxy-lauric acid anilide

4-hydroxy-stearic acid anilide

2,4-bis-octylmercapto-6-(3,5-tert-butyl-4-hydroxyanilino)-s-triazine

octyl-N-(3,5-di-tert-butyl-4-hydroxyphenyl)-carbamate

1.7. Esters of β-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionic acid withmonohydric or polyhydric alcohols, for example,

    ______________________________________                                        methanol      diethylene glycol                                               octadecanol   triethylene glycol                                              1,6-hexanediol                                                                              pentaerythritol                                                 neopentyl glycol                                                                            tris-hydroxyethyl isocyanurate                                  thiodeithylene glycol                                                                       di-hydroxyethyl oxalic acid diamide                             ______________________________________                                    

1.8. Esters of β-(5-tert-butyl-4-hydroxy-3-methylphenyl)-propionic acidwith monohydric or polyhydric alcohols, for example,

    ______________________________________                                        methanol      diethylene glycol                                               octadecanol   triethylene glycol                                              1,6-hexanediol                                                                              pentaerythritol                                                 neopentyl glycol                                                                            tris-hydroxyethyl isocyanurate                                  thiodeithylene glycol                                                                       di-hydroxyethyl oxalic acid diamide                             ______________________________________                                    

1.9. Amides of β-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionic acid forexample,

N,N'-di-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hexamethylenediamine

N,N'-di(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-trimethylenediamine

N,N'-di-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hydrazine

1.10 Diarylamines, for example,

diphenylamine, N-phenyl-1-naphthylamine,N-(4-tert-octylphenyl)-1-naphthylamine,

4,4'-di-tert-octyl-diphenylamine, reaction product ofN-phenylbenzylamine and

2,4,4-trimethylpentene, reaction product of diphenylamine and2,4,4-trimethylpentene, reaction

product of N-phenyl-1-naphthylamine and 2,4,4-trimethylpentene.

2. UV absorbers and light stabilizers

2.1. 2-(2'-Hydroxyphenyl)-benzotriazoles, for example, the 5'-methyl-,3',5'-di-tert-butyl-, 5'-tert-butyl-, 5'-(1,1,3,3-tetramethylbutyl)-,5-chloro-3',5'-di-tert-butyl-, 5-chloro-3'-tert-butyl-5'-methyl-,3'-sec-butyl-5'-tert-butyl-, 4'-octoxy, 3', 5'-di-tert-amyl-,3',5'-bis-(α,α-dimethylbenzyl),3'-tert-butyl-5'-(2-(omega-hydroxy-octa-(ethyleneoxy)carbonyl-ethyl)-,3'-dodecyl-5'-methyl-, and 3'-tert-butyl-5'-(2-octyloxycarbonyl)ethyl-,and dodecylated-5'-methyl derivatives.

2.2. 2-Hydroxy-benzophenones, for example, the 4-hydroxy-, 4-methoxy-,4-octoxy, 4-decyloxy-, 4-dodecyloxy-, 4-benzyloxy, 4,2',4'-trihydroxy-and 2'-hydroxy-4,4'-dimethoxy derivatives.

2.3. Esters of optionally substituted benzoic acids for example, phenylsalicylate, 4-tert-butylphenyl salicylate, octylphenyl salicylate,dibenzoylresorcinol, bis-(4-tert-butylbenzoyl)-resorcinol,benzoylresorcinol, 3,5-di-tert-butyl-4-hydroxybenzoic acid2,4-di-tert-butylphenyl ester and 3,5-di-tert-butyl-4-hydroxybenzoicacid hexadecyl ester.

2.4. Acrylates, for example, α-cyano-β,β-diphenylacrylic acid ethylester or isooctyl ester, α-carbomethoxy-cinnamic acid methyl ester,α-cyano-β-methyl-p-methoxy-cinnamic acid methyl ester or butyl ester,α-carbomethoxy-p-methoxy-cinnamic acid methyl ester,N-(β-carbomethoxy-β-cyanovinyl)-2-methyl-indoline.

2.5. Nickel compounds, for example, nickel complexes of2,2'-thio-bis-[4-(1,1,3,3-tetramethylbutyl)-phenol], such as the 1:1 or1:2 complex, optionally with additional ligands such as n-butylamine,triethanolamine or N-cyclohexyl-diethanolamine, nickeldibutyldithiocarbamate, nickel salts of4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid monoalkyl esters, suchas of the methyl, ethyl or butyl ester, nickel complexes of ketoximessuch as of 2-hydroxy-4-methyl-phenyl undecyl ketoxime, nickel complexesof 1-phenyl-4-lauroyl-5-hydroxy-pyrazole, optionally with additionalligands.

2.6. Sterically hindered amines, for examplebis-(2,2,6,6-tetramethylpiperidyl) sebacate,bis-(1,2,2,6,6-pentamethylpiperidyl) sebacate,n-butyl-3,5-di-tert.butyl-4-hydroxybenzyl malonic acidbis-(1,2,2,6,6-pentanemethylpiperidyl)ester, condensation product of1-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinicacid, condensation product ofN,N'-(2,2,6,6-tetra-methylpiperidyl)-hexamethylenediamine and4-tert-octylamino-2,6-dichloro-s-triazine,tris-(2,2,6,6-tetramethylpiperidyl)-nitrilotriacetate,tetrakis-(2,2,6,6-tetramethyl-4-piperidyl)1,2,3,4-butanetetracarboxylate,1,1'(1,2-ethanediyl)-bis-(3,3,5,5-tetramethylpiperazinone),bis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate.

2.7. Oxalic acid diamides, for example, 4,4'-di-octyloxy-oxanilide,2,2'-di-octyloxy-5,5'-di-tert-butyl-oxanilide,2,2'-di-dodecyloxy-5,5'-di-tert-butyl-oxanilide,2-ethoxy-2'-ethyl-oxanilide, N,N'-bis(3-dimethylaminopropyl)-oxalamide,2-ethoxy-5-tert-butyl-2'-ethyloxanilide and its mixture with2-ethoxy-2'-ethyl-5,4'-di-tert-butyloxanilide and mixtures of ortho- andpara-methoxy- as well as of o- and p-ethoxy-disubstituted oxanilides.

2.8. Hydroxyphenyl-s-triazines, for example2,6-bis-(2,4-dimethylphenyl)-4-(2-hydroxy-4-octyloxyphenyl)-s-triazine;2,6-bis-(2,4-dimethylphenyl)-4-(2,4-dihydroxyphenyl)-s-triazine;2,4-bis(2,4-dihydroxyphenyl)-6-(4-chlorophenyl)-s-triazine;2,4-bis[2-hydroxy-4-(2-hydroxyethoxy)phenyl]-6-(4-chlorophenyl)-s-triazine;2,4-bis[2-hydroxy-4-(2-hydroxy-4-(2-hydroxyethoxy)phenyl]-6-(2,4-dimethylphenyl)-s-triazine;2,4-bis[2-hydroxy-4-(2-hydroxyethoxy)-phenyl]-6-(4-bromophenyl)-s-triazine;2,4-bis[2-hydroxy-4-(2-acetoxyethoxy)phenyl]-6-(4-chlorophenyl)-s-triazine,2,4-bis(2,4-dihydroxyphenyl)-6-(2,4-dimethylphenyl)-s-triazine.

3. Metal deactivators, for example, N,N'-diphenyloxalic acid diamide,N-salicylal-N'-salicyloylhydrazine, N,N'-bis-salicyloylhydrazine,N,N'-bis-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hydrazine,3-salicyloylamino-1,2,4-triazole, bis-benzylidene-oxalic aciddihydrazide.

4. Phosphites and phosphonites, for example, triphenyl phosphite,diphenylalkyl phosphites, phenyldialkyl phosphites, tri-(nonylphenyl)phosphite, trilauryl phosphite, trioctadecyl phosphite,di-stearyl-pentaerythritol diphosphite, tris-(2,4-di-tert-butylphenyl)phosphite, di-isodecylpentaerythritol diphosphite,di-(2,4-di-tert-butylphenyl)pentaerythritol diphosphite,tristearylsorbitol triphosphite, tetrakis-(2,4-di-tert-butylphenyl)4,4'-diphenylylenediphosphonite.

5. Compounds which destroy peroxide, for example, esters ofβ-thiodipropionic acid, for example the lauryl, stearyl, myristyl ortridecyl esters, mercapto-benzimidazole or the zinc salt of2-mercaptobenzimidazole, zinc dibutyl-dithiocarbamate, dioctadecyldisulfide, pentaerythritol tetrakis-(β-dodecylmercapto)-propionate.

6. Hydroxylamines, for example, N,N-dibenzylhydroxylamine,N,N-diethylhydroxylamine, N,N-dioctylhydroxylamine,N,N-dilaurylhydroxylamine, N,N-ditetradecylhydroxylamine,N,N-dihexadecylhydroxylamine, N,N-dioctadecylhydroxylamine,N-hexadecyl-N-octadecylhydroxylamine,N-heptadecyl-N-octadecylhydroxylamine, N,N-dialkylhydroxylamine derivedfrom hydrogenated tallow amine.

7. Nitrones, for example, N-benzyl-alpha-phenyl nitrone,N-ethyl-alpha-methyl nitrone, N-octyl-alpha-heptyl nitrone,N-lauryl-alpha-undecyl nitrone, N-tetradecyl-alpha-tridecyl nitrone,N-hexadecyl-alpha-pentadecyl nitrone,N-octadecyl-alpha-heptadecylnitrone, N-hexadecyl-alpha-heptadecylnitrone, N-octadecyl-alpha-pentadecyl nitrone,N-heptadecyl-alpha-heptadecyl nitrone, N-octadecyl-alpha-hexadecylnitrone, nitrone derived from N,N-dialkylhydroxylamine derived fromhydrogenated tallow amine.

8. Polyamide stabilizers, for example copper salts in combination withiodides and/or phosphorus compounds and salts of divalent manganese.

9. Basic co-stabilizers, for example, melamine, polyvinylpyrrolidone,dicyandiamide, triallyl cyanurate, urea derivatives, hydrazinederivatives, amines, polyamides, polyurethanes, alkali metal salts andalkaline earth metal salts of higher fatty acids for example Castearate, Zn stearate, Mg stearate, Na ricinoleate and K palmitate,antimony pyrocatecholate or zinc pyrocatecholate.

10. Nucleating agents, for example, 4-tert-butyl-benzoic acid, adipicacid, diphenylacetic acid.

11. Fillers and reinforcing agents, for example, calcium carbonate,silicates, glass fibers, asbestos, talc, kaolin, mica, barium sulfate,metal oxides and hydroxides, carbon black, graphite.

12. Other additives, for example, plasticizers, lubricants, emulsifiers,pigments, optical brighteners, flameproofing agents, anti-static agents,blowing agents and thiosynergists such as dilauryl thiodipropionate ordistearyl thiodipropionate.

The phenolic antioxidant of particular interest is selected from thegroup consisting of n-octadecyl3,5-di-tert-butyl-4-hydroxyhydrocinnamate, neopentanetetrayltetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinammate), di-n-octadecyl3,5-di-tert-butyl-4-hydroxybenzylphosphonate,1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate,thiodiethylene bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate),1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-benzene,3,6-dioxaoctamethylenebis(3-methyl-5-tert-butyl-4-hydroxyhydrocinnamate),2,6-di-tert-butyl-p-cresol,2,2'-ethylidene-bis(4,6-di-tert-butylphenol),1,3,5-tris(2,6-dimethyl-4-tert-butyl-3-hydroxybenzyl)isocynurate,1,1,3,-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane,1,3,5-tris[2-(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyloxy)ethyl]isocyanurate,3,5-di-(3,5-di-tert-butyl-4-hydroxybenzyl)mesitol, hexamethylenebis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate),1-(3,5-di-tert-butyl-4-hydroxyanilino)-3,5-di(octylthio)-s-triazine,N,N'-hexamethylene-bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamamide),calcium bis(ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate),ethylene bis[3,3-di(3-tert-butyl-4-hydroxyphenyl)butyrate], octyl3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate,bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyl)hydrazide, andN,N'-bis[2-(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyloxy)-ethyl]-oxamide.

A most preferred phenolic antioxidant is neopentanetetrayltetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate), n-octadecyl3,5-di-tert-butyl-4-hydroxyhydrocinnamate,1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene,1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate,2,6-di-tert-butyl-p-cresol or2,2'-ethylidene-bis(4,6-di-tert-butylphenol).

The hindered amine compound of particular interest is selected from thegroup consisting of bis(2,2,6,6-tetramethylpiperidin-4-yl) sebacate,bis(1,2,2,6,6-pentamethylpiperidin-4-yl) sebacate,di(1,2,2,6,6-pentamethylpiperidin-4-yl)(3,5-di-tert-butyl-4-hydroxybenzyl)butylmalonate,4-benzoyl-2,2,6,6-tetramethylpiperidine,4-stearyloxy-2,2,6,6-tetramethylpiperidine,3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triaza-spiro[4.5]decane-2,4-dione,tris(2,2,6,6-tetramethylpiperidin-4-yl) nitrilotriacetate,1,2-bis(2,2,6,6-tetramethyl-3-oxopiperazin-4-yl)ethane,2,2,4,4-tetramethyl-7-oxa-3,20-diaza-21-oxodispiro[5.1.11.2]heneicosane, polycondensation product of2,4-dichloro-6-tert-octylamino-s-triazine and4,4'-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine),polycondensation product of1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinicacid, polycondensation product of4,4'-hexamethylenebis-(amino-2,2,6,6-tetra-methylpiperidine) and1,2-dibromoethane, tetrakis(2,2,6,6-tetramethylpiperidin-4-yl)1,2,3,4-butanetetracarboxylate,tetrakis(1,2,2,6,6-pentamethylpiperidin-4-yl)1,2,3,4-butanetetracarboxylate, polycondensation product of2,4-dichloro-6-morpholino-s-triazine and4,4'-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine),N,N',N",N"'-tetrakis[(4,6-bis(butyl-2,2,6,6-tetramethyl-piperidin-4-yl)-amino-s-triazin-2-yl]-1,10-diamino-4,7-diazadecane,mixed[2,2,6,6-tetramethylpiperidin-4-yl/β,β,β',β'-tetramethyl-3,9-(2,4,8,10-tetraoxaspiro[5.5]-undecane)diethyl] 1,2,3,4-butanetetracarboxylate, mixed[1,2,2,6,6-pentamethylpiperidin-4-yl/β,β,β',β'-tetramethyl-3,9-(2,4,8,10-tetraoxaspiro[5.5]-undecane)diethyl]1,2,3,4-butanetetracarboxylate, octamethylenebis(2,2,6,6-tetramethylpiperidin-4-carboxylate),4,4'-ethylenebis(2,2,6,6-tetramethylpiperazin-3-one) andbis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate.

A most preferred hindered amine compound isbis(2,2,6,6-tetramethylpiperidin-4-yl) sebacate, the polycondensationproduct of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperdine andsuccinic acid, the polycondensation product of2,4-dichloro-6-tert-octylamino-s-triazine and4,4'-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine),N,N',N",N"'-tetrakis[(4,6-bis(butyl-(2,2,6,6-tetramethyl-piperidin-4-yl)amino)-s-triazine-2-yl]-1,10-diamino-4,7-diazadecaneor bis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate.

The following examples are presented for the purpose of illustrationonly and are not to be construed as limiting the nature or scope of theinstant invention in any manner whatsoever.

EXAMPLE 1 1,4-Bis(2,6-diphenylpiperidin-1-yl)-2-butene

A solution of 2,6-diphenylpiperidine [3.0 g, 12.6 mmol; prepared by themethod of V. Baliah et al., Indian J. Chem., 16B, 1965 (1978)] and1,4-but-2-enediol diacetate (1.1 g, 6.3 mmol) in tetrahydrofuran (20 ml,THF) is treated with tetrakis(triphenylphosphine)palladium (0) (0.65 g,0.6 mmol) and stirred at room temperature overnight. The reactionmixture is concentrated in vacuo to a solid that is redissolved in THF(100 ml) and treated with 20% aqueous sodium hydroxide (25 ml). Themixture is stirred for one hour, concentrated, and extracted withdiethyl ether. The ether extracts are dried and concentrated giving anorange solid which is purified by crystallization from methanol to yield2.02 g (61%) of the title compound as a white solid melting at 197°-200°C.

Analysis: Calcd for C₃₈ H₄₂ N₂ : C, 86.6; H, 8.0; N, 5.3. Found: C,86.7; H, 8.0; N, 5.2.

EXAMPLE 2 1-(2,6-Diphenylpiperidin-1-yl)-4-dibenzylamino-2-butene

A solution of dibenzylamine (40 g, 0.20 mol) and 1,4-but-2-enedioldiacetate (105 g, 0.61 mol) in THF (150 ml) is treated withtetrakis(triphenylphosphine)palladium (0) (1 g, 0.9 mmol) and stirred atroom temperature overnight. The reaction mixture is concentrated invacuo and the excess 1,4-but-2-enediol is removed by bulb-to-bulbdistillation (80°-90° C., 1 mm). The residue is purified by elutingthrough a short plug of silica gel (1:1, ethyl acetate:hexanes). 59.2 g(95%) of 1-acetoxy-4-dibenzylamino-2-butene is obtained.

A solution of 1-acetoxy-4-dibenzylamino-2-butene (3.0 g, 9.8 mmol) and2,6-diphenylpiperidine (2.3 g, 9.8 mmol) in THF (25 ml) is treated withtetrakis(triphenylphosphine)palladium (0) (0.5 g, 0.45 mmol) and stirredat room temperature overnight. The reaction mixture is concentrated invacuo. The residue is redissolved in THF (100 ml) and treated with 20%aqueous sodium hydroxide (25 ml). The mixture is stirred for one hour,concentrated, and extracted with diethyl ether. The ether extracts aredried and concentrated to give an orange oil which is purified bychromatography (silica gel; 5% ethyl acetate in hexanes) to give thetitle compound in a yield of 2.8 g (59%) as a clear oil. MS m/z 486 (M⁺)

EXAMPLE 3 Process Stabilization of Dynamically CrosslinkedPolypropylene/Nitrile Rubber

To a Brabender Plasticorder heated to 190° C. is added 55 grams ofdynamically corsslinked polypropylene/nitrile rubber (GEOLAST,Monsanto). The polymer is mixed under nitrogen for 3 minutes at 30 rpmand then 2.2 grams (4% by weight of the resin blend) of the testcompound is added under nitrogen and mixed into the resin blend at 90rpm for 7 minutes. The test sample is then removed from the Brabenderand flattened in a cold press.

The test sample is then compression molded into plaques (4"×4"×60 mils;10.16 cm×10.16 cm×1.524 mm) at 200° C. for 4 minutes at 2000 psi (140Kg/cm²) and then 4 minutes at 50,000 psi (3500 Kg/cm²).

The plaques are then cut into tensile bars and oven aged in a forceddraft oven at 135° C. for 7 days. The aged samples are tested for %retention of elongation according to ASTM

The % elongation of triplicate bars are measured before and after ovenaging. The greater the % retention of the % elongation, the moreeffective is the stabilizer compound.

The instant compounds of Examples 1 and 2 provide the GEOLAST resin witheffective stabilization against thermal oxidative degradation.

What is claimed is:
 1. A compound of formula I

    T--CH.sub.2 --CH═CH--CH.sub.2 --T                      (I)

wherein T is a group of formula III, IV, V or VI ##STR2## where Ar₁ andAr₂ are independently carbocyclic aryl of 6 to 10 carbon atoms; or saidaryl substituted by one to three substituents selected from the groupconsisting of alkyl of 1 to 20 carbon atoms, cycloalkyl of 5 to 12carbon atoms, phenylalkyl of 7 to 15 carbon atoms, --COOG₁ where G₁ ishydrogen or alkyl of 1 to 20 carbon atoms, --COG₂ where G₂ is alkyl of 1to 20 carbon atoms, --NR₅ R₆ where R₅ and R₆ are independently hydrogenor alkyl of 1 to 20 carbon atoms, --SG₃ where G₃ is carbocyclic aryl of6 to 10 carbon atoms or alkyl of 1 to 20 carbon atoms, --OH, --OCH₃,--CN, --CF₃, --NO₂, --F, --Cl, --Br or -- I; R₁, R₂, R₃ and R₄ areindependently hydrogen; a linear or branched alkyl of 1 to 30 carbonatoms; said alkyl terminated with --OR₇, --NR₈ R₉, --SR₁₀, --COOR₁₁ or--CONR₁₂ R₁₃, where R₇, R₈, R₉, R₁₀ and R₁₁ are independently hydrogen,alkyl of 1 to 20 carbon atoms or alkenyl of 3 to 18 carbon atoms, andR₁₂ and R₁₃ are independently hydrogen or the same meaning as R₁₁ ; orsaid alkyl interrupted by one or two --O--, --S--, --SO--, --SO₂ --,--CO--, --COO--, --OCO--, --CONR₁₄ --, --NR₁₄ CO-- or --NR₁₅ -- whereR₁₄ and R₁₅ have the same meaning as R₁₂ ; alkenyl of 3 to 20 carbonatoms; or carbocyclic aryl of 6 to 10 carbon atoms; L₁ is hydrogen,--OR₂₅ where R₂₅ is hydrogen or alkyl of 1 to 30 carbon atoms, --NR₂₆R₂₇, --OCOR₂₈, --NCOR₂₉ where R₂₆, R₂₇, R₂₈ and R₂₉ have the samemeaning as R₂₅ ; L₂ and L₃ are independently --Y₁ --R₃₀ or --Z₁ --R₃₁where Y₁ and Z₁ are independently --O--, --S-- or --NR₂₆ --, and R₃₀ andR₃₁ are hydrogen or alkyl of 1 to 30 carbon atoms; and n is 0 or 1, Y₂and Z₂ are independently --O--, --S-- or --NR₂₆ --, and R₃₂, R₃₃, R₃₄,R₃₅, R₃₆ and R₃₇ are independently hydrogen or alkyl of 1 to 30 carbonatoms.
 2. A compound according to claim 1 wherein Ar₁ and Ar₂ arephenyl.
 3. A compound according to claim 1 wherein R₁, R₂, R₃ and R₄ areindependently hydrogen or methyl.
 4. A compound according to claim 3wherein R₁, R₂, R₃ and R₄ are each hydrogen.
 5. A compound according toclaim 1 wherein T is a structure of formula III where L₁ is hydrogen. 6.The compound according to claim 1 which is1,4-bis(2,6-diphenylpiperidin-1yl)-2-butene.